I«-Bromoaniline

Intermediates benzene to nitrobenzene to i-bromonitrobenzene to i-bromoaniline to m-bromophenol. Reagents HNO3, H2SO4 Br2, FeBr3 Fe, HCl then HO NaN02, H2SO4, H2O, then heat in H2O. 

Reagents and conditions i, p-bromoaniline or p-aminobenzonitrile, CHCI3 ii, hv, toluene/methanol (10 1) Scheme 10... 

Complexes of Rh, Pt, and Pd with the same ligands were active in the biphasic hydrogenation of chloro- and bromonitrobenzenes. At 80-100 °C and 20 bar H2 pressure the main products were the corresponding chloro-and bromoanilines, up to 99.8 % yield (Scheme 10.5) [12]. The selectivity of similar reactions catalyzed by a Rh/TPPTS was only about 90 %, i.e. the attached cyclodextrin moiety further decreased the extent of hydrodehalogenation, probably by complexation of the halonitroaromatic substrate. 

For weakly basic amines, i.e. anilines with poly nitro groups, e.g. 2, 4,-dintro-6-bromoaniline, and also most heterocyclic amines, an alternative method must be adopted using nitrosylsulfuric acid. This diazotising medium can be made by dissolving sodium nitrite in concentrated sulfuric acid, but is also available preformed from chemical suppliers. The weakly basic amine is added gradually to the nitrosyl-sulfuric acid with cooling, and after reaction is complete the mixture is poured into ice and water to give a solution of the diazonium salt. 

Copper-catalyzed coupling reaction of 2-bromoanilines and pipecoli-nic acid provided 6,6fl,7,8,9,10-hexahydro-5H-pyrido[l,2-a]quinoxalin-6-ones 392 (09BML4119). Using [Pd(r/3-C3H5)Cl2]2 with (2-biphenyl)di-ferf-butylphosphine catalyst system and Cu(I)Br gave lower yields. 

The arylstannylation of the aniline skeleton using o-, m- or p-brorno-A V-dirnclhy I anilines has been reported (equation 94)139. In the case of the three bromoanilines, a modified process was used (Scheme 20)139. 

Nicholson, J.K., Lindon, J.C., Scarfe, G., Wilson, I.D., Abou-Shakra, F., Castro-Perez, J., Eaton, A., Preece, S. High-performance liquid chromatography and inductively coupled plasma mass spectrometry (HPLC ICP MS) for the analysis of xenobiotic metabolites in rat urine application to the metabolites of 4-bromoaniline. Analyst 125, 235-236 (2000)... 

Show the products from reaction of p-bromoaniline with the following reagents (a) Excess CH ,I (b) HCl (c) HNO2, H2SO4... 

In 1976, Hegedus et al. described the synthesis of indoles using a Pd-assisted intramolecular amination of olefins, which tolerated a range of functionalities [8a, 114]. For example, the requisite o-allylaniline 119 was prepared in high yield by the reaction of 5-methoxy-carbonyl-2-bromoaniline with n-ally I nickel bromide. Addition of 119 to a suspension of stoichiometric PdCl2(CH3CN)2 in THF produced a yellow precipitate (the putative intermediate 121), which upon treatment with Et, N gave rise to indole 120 and deposited metallic palladium. 

As has been pointed out in Section I, 2, when R and R" differ, the two isomers (A and B) permitted by the classical formulation cannot be isolated (because of the chelated structure of the formazans). This phenomenon, so very characteristic of the formazans, is also encountered in the formazans of sugars. The mono-p-bromo derivative of n-galactose diphenylformazan was prepared by two routes one was by causing n-galactose p-bromo-phenylhydrazone to react with diazotized aniline the other, by coupling D-galactose phenylhydrazone with diazotized p-bromoaniline as follows. 

Suggest syntheses for each of the following compounds from the starting material indicated ta) 3-bromoaniline from benzene (b) 3-nitrobenzoic acid from toluene (c) 4-nitrobenzoic acid from toluene (d) 4-methylbenzophenone from benzoic acid (e) I-methoxy-2.4-dinitrobenzene from chlorobenzene. 

The reaction between [Mo(0)Cl2(Tp )] and 4-bromoaniline in refluxing toluene gave geometric isomers of [Mo(0)Cl(Tp )]( i-0)[Mo(Cl)(=NCgH4Br)Tp ], both structurally characterized, whereas a similar reaction between [Mo(0)Cl2(Tp )] and 4-chloroaniline yielded only one product, [MoTp (0)Cl]( x-0)[MoTp -(C1)(=NC6H4C1)].71... 

Indole synthesis. A novel route to 4-iodoindoles involves reaction of N-allyl-N-bcnzyl-2-bromoaniline (I) with this zirconoccnc to form the zirconacycle 2, which is converted into 3 by iodination and elimination. This product undergoes ene reactions... 

Reactions suitable for the kinetics aiming at the purpose mentioned above needs to satisfy one condition. The TST must be valid for a fairly wide range of pressure and temperature. Furthermore it is desirable that the reactant can be generated in situ and the reaction can be followed spectroscopically to obtain reliable rate constants. As the first set of reactions, thermal ZfE isomerization of three N-benzylideneanilines (benzaldehyde anUs), i.e. N-[4-(dimethylamino) benzylidene]-4-nitroaniline (DBNA), N-[4-(dimethylamino)benzylidene]-4-ethoxy-carbonylaniline (DBEA), and N-[4-(dimethylamino)benzylidene]-4-bromoaniline (DBBA), and two push-pull substituted azobenzenes, i.e. 4-(dimethylamino)-4 -nitroazobenzene (DNAB) and 4 -(dimethylamino)-2-methoxy-4-nitroazobenzene (DMNAB) as shown in Scheme 3.2 were selected. 

Dimethoxyaniline 4-Chloropyridine 4-Bromoaniline 1-Aminofluorene I-Amino-6-methoxynaphthalene l-Aminonaphthalene... 

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